International Journal of Emerging Technology and Advanced Engineering

Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 1, January 2013)

ALKALI Activated FLY-ASH Based Geopolymer Concrete

Ammar Motorwala1, Vineet Shah2, Ravishankar Kammula3, Praveena Nannapaneni4, Prof. D. B. Raijiwala5
1
Department of Applied Mechanics, SVNIT-Surat, Gujarat-395007
2
Department of Civil Engineering, IIT-Delhi
3,4
Department of Civil Engineering, SVNIT-Surat, Gujarat-395007
5
Associate Professor, Department of Applied Mechanics, SVNIT-Surat, Gujarat-395007
Abstract- Considering the increasing demand for
developing alternative construction materials, due to the
growing environmental concerns, this paper discusses the
feasibility of alkali activated geo-polymer concrete, as a
future construction material. The main objective of this
study involves observation of structural behaviours of the
fresh fly ash-based geo-polymer concrete, understanding
the basic mixture proportioning of fly ash-based geo-
polymer concrete and evaluating various economic
considerations.
Keywords- Alkali activated fly-ash based geo-polymer,
construction material for green building, geo-polymer
concrete, eco-friendly construction material, low calcium
based geo-polymer concrete.
I. INTRODUCTION
Concrete usage around the world is second only to
water and Ordinary Portland Cement (OPC) is
conventionally used as the primary binder to produce
concrete. The environmental issues associated with the
production of OPC are too many. The cement industry is
held responsible for some of the CO2 emissions. The
amount of the carbon dioxide released during the
manufacturing of OPC due to the calcination of
limestone and combustion of fossil fuel is in the order of
one ton for every ton of OPC produced. In addition,
the extent of energy required to produce OPC is only
next to steel and aluminium.
The demand for Portland cement is increasing day by
day and hence, efforts are being made in the construction
industry to address this by utilising supplementary
materials and developing alternative binders in concrete;
the application of geo-polymer technology is one such
alternative. The abundant availability of fly ash
worldwide creates opportunity to utilise this by-product
of burning coal, as a substitute for OPC to manufacture
concrete. When used as a partial replacement of OPC, in
the presence of water and in ambient temperature, fly ash
reacts with the calcium hydroxide during the hydration
process of OPC to form the calcium silicate hydrate (C-
S-H) gel.
In 1978, Davidovits (1999) proposed that binders
could be produced by a polymeric reaction of alkaline
liquids with the silicon and the aluminium in source
materials of geological origin or by-product materials
such as fly ash and rice husk ash. He termed these
binders as geo-polymers.
Palomo et al (1999) suggested that pozzolans such as
blast furnace slag might be activated using alkaline
liquids to form a binder and hence totally replace the use
of OPC in concrete. Hence, in this paper an effort is
made to identify and study the effect of salient
parameters that affects the properties of low-calcium fly
ash-based geo-polymer concrete and the properties of
concrete at varied concentrations of alkali solutions and
how the change in temperature affects the strength
characteristics.
II. GEOPOLYMER
Geo-polymer is a term covering a class of
synthetic alumino-silicate materials with potential use in
a number of areas, essentially as a replacement
for Portland cement and for advanced high-tech
composites, ceramic applications or as a form of cast
stone. The name Geo-polymer was first applied to these
materials by Joseph Davidovits in the 1970s, although
similar materials had been developed in the
former Soviet Union since the 1950s, originally under the
name "soil cements". However, this name never found
widespread usage in the English language, as it is more
often applied to the description of soils which are
consolidated with a small amount of Portland cement to
enhance strength and stability. Geo-polymer cements are
an example of the broader class of alkali-activated
binders, which also includes alkali-
activated metallurgical slags and other related materials
A. Constituents of geo-polymer concrete
There are two main constituents of geo-polymers,
namely the source materials and the alkaline liquids.
The source materials for geo-polymers based on
alumina-silicate should be rich in silicon (Si) and
aluminium (Al). These could be natural minerals such
as kaolinite, clays, etc. Alternatively, by-product
materials such as fly ash, silica fume, slag, rice-
husk ash, red mud, etc. could be used as source
materials. The choice of the source materials for making
geo-polymers depends on factors such as availability,
cost, type of application, and specific demand of the end
users.

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B. Fly Ash
According to the American Concrete Institute
(ACI) Committee 116R, fly ash is defined as the
finely divided residue that results from the combustion
of ground or powdered coal and that is transported by
flue gasses from the combustion zone to the particle
removal system (ACI Committee 232 2004). Fly ash is
removed from the combustion gases by the dust
collection system, either mechanically or by using
electrostatic precipitators, before they are discharged to
the atmosphere. Fly ash particles are typically spherical,
finer than Portland cement and lime, ranging in diameter
from less than 1 m to no more than 150 m.
The chemical composition is mainly composed of the
oxides of silicon (SiO2), aluminium (Al2O3), iron
(Fe2O3), and calcium (CaO), whereas magnesium,
potassium, sodium, titanium, and sulphur are also present
in a lesser amount.
Figure 1 Ungraded fly-ash
Figure 2 Graded fly-ash
160
The characteristics of fly ash that generally considered
are loss on ignition (LOI), fineness and uniformity. LOI
is a measurement of un-burnt carbon remaining in the
ash. Fineness of fly ash mostly depends on the operating
conditions of coal crushers and the grinding process of
the coal itself. Finer gradation generally results in a more
reactive ash and contains less carbon.
C. Use of Fly Ash in Concrete
Fly ash plays the role of an artificial pozzolan,
where its silicon dioxide content reacts with the
calcium hydroxide from the cement hydration process to
form the calcium silicate hydrate (C- S-H) gel. The
spherical shape of fly ash often helps to improve the
workability of the fresh concrete, while its small
particle size also plays as filler of voids in the
concrete, hence to produce dense and durable concrete.
An important achievement in the use of fly ash in
concrete is the development of high volume fly ash
(HVFA) concrete that successfully replaces the use of
OPC in concrete up to 60% and yet possesses excellent
mechanical properties with enhanced durability
performance.
D. Alkaline Liquids
The most common alkaline liquid used in geo-
polymerisation is a combination of sodium hydroxide
(NaOH) or potassium hydroxide (KOH) and sodium
silicate or potassium silicate (Davidovits 1999; Palomo et
al. 1999; Barbosa et al. 2000; Xu and van Deventer 2000;
Swanepoel and Strydom 2002; Xu and van Deventer
2002). The use of a single alkaline activator has been
reported (Palomo et al. 1999; Teixeira- Pinto et al. 2002),
Palomo et al (1999) concluded that the type of alkaline
liquid plays an important role in the polymerisation
process. Reactions occur at a high rate when the alkaline
liquid contains soluble silicate, either sodium or
potassium silicate, compared to the use of only alkaline
hydroxides. Xu and van Deventer (2000) confirmed that
the addition of sodium silicate solution to the sodium
hydroxide solution as the alkaline liquid enhanced the
reaction between the source material and the solution.
Furthermore, after a study of the geo-polymerisation of
sixteen natural Al-Si minerals, they found that generally
the NaOH solution caused a higher extent of dissolution
of minerals than the KOH solution.
E. Super Plasticisers:
In order to improve the workability of fresh concrete,
high-range water-reducing naphthalene based super
plasticiser was added to the mixture. The dosage of super
plasticizer also has an effect on the compressive strength
of the concrete.
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The specific super plasticizer used in the mixture made F. Polymerisation Process
for the project is Sikament-581.As a super plasticizer it Geo-polymers are members of the family of
substantially improved the workability without increasing inorganic polymers. The chemical composition of the
the amount of water and hence reducing the risk of geopolymer material is similar to natural zeolitic
segregation. It results in normal set even when materials, but the microstructure is amorphous. The
overdosed. It gives a good surface finish and as it is polymerization process involves a substantially fast
chloride free it doesnt attack reinforcement or pre- chemical reaction under alkaline condition on Si- Al
stressed cables if any. Apart from this, various other minerals, which results in a three-dimensional polymeric
super plasticisers, which can be used, are categorized as chain and ring structure consisting of Si-O- Al-O bonds
Super Plasticiser A (Naphthalene
Formaldehyde Condensate) M n [-(SiO2) z AlO2] n . wH 2O
Super Plasticiser B (Sulphonated Melamine Where: M = the alkaline element or cation such as
Formaldehyde Condensate) potassium, sodium or calcium;
Super Plasticizer C (Aqueous De The symbol indicates the presence of a bond,
Policarboxilato) n is the degree of poly-condensation or
Super Plasticizer D (Aqueous Solution of Ligno polymerisation;
Sulphonate) z is 1, 2,3, or higher, up to 32.
The main chemical base is Modified Naphthalene The schematic formation of geopolymer material
Formaldehyde and the dosage varies from 0.6-2% of the can be shown as described by
weight of fly ash.
+ + -
n(Si2O5,Al2O2)+2nSiO2+4nH2O+NaOH or KOH Na ,K + n(OH)3-Si-O-Al -O-Si-(OH)3
(Si-Al materials)
(OH)2

- -
n(OH)3-Si-O-Al -O-Si-(OH)3 + NaOH or KOH (Na+,K+)-(-Si-O-Al -O-Si-O-) + 4nH2O (OH)2

O O O

The chemical reaction may comprise the following G. Chemical composition of the geo-polymers
steps Differences due to various conditions of the alkaline
Dissolution of Si and Al atoms from the source activation may be found on the FTIR spectra.
material through the action of hydroxide ions.
Transportation or orientation or condensation
of precursor ions into monomers.
Setting or poly-condensation/polymerisation
of monomers into polymeric structures.
However, these three steps can overlap with each other
and occur almost simultaneously, thus making it
difficult to isolate and examine each of them
separately (Palomo et al. 1999).
The last term in Equation reveals that water is released
during the chemical reaction that occurs in the formation
of geo-polymers. This water, expelled from the geo-
polymer matrix during the curing and further drying
periods, leaves behind discontinuous Nano-pores in the Figure 3 Beginning of the geo-polymers phase development on the
matrix, which provide benefits to the performance of surface of the fly ash particle
geo-polymers. The water in a geo-polymer mixture, The band corresponding to Si-O and Al-O vibrations
therefore, plays no role in the chemical reaction that
can be observed in the original fly ash at 1,080-1,090
takes place; it merely provides the workability to the
-1
mixture during handling. This is in contrast to the cm but this band is displaced towards lower values in
chemical reaction of water in a Portland cement mixture the geo-polymers.
during the hydration process.
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The shift is interpreted as a consequence of the Al
penetration into the original structure of the Si-O-S
skeleton (an analogous phenomenon was observed in
zeolites). The more pronounced the shift, the greater the
extent of the Al penetration from the glassy parts of the
4-
fly ash into the [SiO4] skeleton.
The geo-polymerization process (alkaline activation of
fly ashes in the aqueous environment at pH>12)
accompanied by the hardening of the material is different
from the hydration processes of inorganic binders (e.g.
Portland cement). This process obviously takes place
predominantly via solution when, first, the fly ash
particles are dissolved and a new geo-polymers
structure is then formed starting from the solution
(Fig 3).
In addition to the preparation conditions also the
presence of Ca atoms entering the Si- O-Al-O skeleton
and compensating the charge on Al atoms plays an
important role.
Figure 4 Detailed character of the geo-polymers (the paste w = 0.27,
fracture surface, after 28 days)
A prevailing part of water gets lost during the heating
o
at a temperature of 150-200 C. No crystalline hydrates
could be detected in the geo-polymers microstructure.
Therefore, the geo-polymer can be characterized as
three-dimensional inorganic polymer with a summary
formula:
Mn [-(Si-O)z Al-O]n . w(H2O).
III. EXPERIMENTAL DEDUCTIONS
A. Mixture Proportions:
The mixture proportion of concrete contains coarse
aggregate, fine aggregate, fly ash, Sodium silicate
solution and NaOH solution. Three different mixtures
with 8M, 10M, 12M and 14M were prepared and
compressive strengths of these sample cubes were
measured.
The sodium hydroxide (NaOH) solids were dissolved
in water to make the solution. The mass of NaOH solids
in a solution varied depending on the concentration of
the solution expressed in terms of molar, M.
For instance, NaOH solution with a concentration of
8M consisted of 8x40 = 320 grams of NaOH solids
(in flake or pellet form) per litre of the solution, where
40 is the molecular weight of NaOH. Similarly, the mass
of NaOH solids per kg of the solution for 14M
concentration was measured as 404 grams.
The sodium silicate solution and the sodium hydroxide
solution were mixed together at least one day prior to
use to prepare the alkaline liquid. On the day of casting
of the specimens, the alkaline liquid was mixed together
with the super plasticizer and the extra water (if any) to
prepare the liquid component of the mixture.

These charges are usually compensated by Na+ ions.

Nevertheless Ca+2 ions may probably interconnect
individual Si-O-Al-O chains thus giving rise to a stronger
structure characterized by higher strength values
resulting from the alkaline activation of fly ashes in
presence of Ca-containing materials.
Water is present in the geo-polymers structure as this
is revealed by the GTA curves. Water obviously occurs
in the form of free water but water molecules also exist
-
inside the structure; furthermore, OH groups are also
present.
Figure 5 Schematic diagrams for mixing process

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Table 1
Mixture proportions

Aggregates (kg) Water

Fly-ash Strength
Mixture No. content
20mm 10mm 4.75mm (kg) (N/mm2)
(litres)
1 5 12 7.3 6 2 1.09
2 5 12 7.3 6 2.25 3.48
3 10.2 6.8 7.3 4 2.1 30.95
4 12 5 7.3 4.8 2.3 24.4
5 12 5 7.3 4.8 2 15.26
6 12 5 7.3 4.5 2.1 3.7
7 12 5 7.3 4.8 2.2 2.18
8 12 5 7.3 4.5 2 1.74

Table 2
Mixture proportion

Sodium Potassium
Mixture Sodium Silicate plasticizer Strength
Molarities Hydroxide Hydroxide
No. (kg) (ml) (N/mm2)
(kg) (kg)
1 10 M 0.173 0 1.657 90 1.09
2 12 M 0.238 0 1.657 48 3.48
3 14 M 0.267 0 1.657 60 30.95
4 14 M 0.267 0 1.657 50 24.4
5 16 M 0.293 0 1.657 50 15.26
6 16 M 0.293 0 1.657 50 3.7
7 0.314 1.657 50 2.18
8 0.314 1.657 50 1.74

IV. EFFECT O F S ALIENT P ARAMETERS B. Concentration of Sodium Hydroxide (NaOH) Solution

Mixtures were made to study the effect of
A. Ratio of Alkaline Liquid-to-Fly Ash
concentration of sodium hydroxide solution on the
The ratio of alkaline liquid-to-fly ash, by mass, was compressive strength of concrete. Complete details of
not varied. This ratio was taken as 0.4. these mixtures and their properties are given in Table.
The test cubes were left at ambient conditions for about
30 minutes prior to start of dry curing in an oven. The
Strength curing time was 24 hours at various temperatures. The
measured 7th day compressive strengths of test cubes are
given in Table.
compressive strength

40

20
N/mm2

0
6 4 4.8
Flyash (Kg)

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D. Curing Temperature
Sodium Hydroxide (Kg) Higher curing temperature resulted in larger
compressive strength, although an increase in the curing
40 temperature beyond 80 degrees Centigrade did not
compressive strength

30 increase the compressive strength substantially. Three

20 different curing temperatures were used, i.e. 25, 80 and
N/mm2

10 100 degrees Centigrade. Curing was performed in an

0 Sodium oven for 24 hours. The results shown in Table confirm
that higher curing temperature resulted in higher
compressive strength.

NaOH Curing Compressive

Mixture Temperature in strength
O
C (MPa)
C. Effect of Molarity of Alkaline Solutions
1 25 0.872
Mixture Concentration Ratio of Compressive
2 60 2.6
of NaOH Sodium strength at 7th
solution Silicate day in Mpa 3 80 30.95
(In molars) to (Cured at 80
0
NaOH C) E. Addition of Super plasticizer
solution
In fresh state, the geo-polymer concrete has a stiff
1 10 M 2.5 1.5 consistency. Although adequate compaction was
achievable, an improvement in the workability was
2 12 M 2.5 2.6 considered as desirable. As the concentration of Super
plasticizer increases the amount of water required
3 14 M 2.5 26.67 decreases.
Series of tests, performed to study the effect of super
4 16 M 2.5 25.28 plasticizer on fly-ash concrete indicated that super
plasticizer improved the workability of the fresh concrete
but had very little effect on the compressive strength up
to 2% of this admixture to the amount of fly ash by mass.
35 F. Water Content of Mixture
compressive strength

30 In ordinary Portland cement (OPC) concrete, water in

25 the mixture chemically reacts with the cement to produce
N/mm2

20 a paste that binds the aggregates. In contrast, the water in

15 a low-calcium fly ash-based geo-polymer concrete
10 mixture does not cause a chemical reaction. In fact, the
Strength
5 chemical reaction that occurs in geo-polymers produces
0 water that is eventually expelled from the binder.
10 12 14 16 G. Density
M M M M The density of concrete primarily depends on the unit
Molarity mass of aggregates used in the mixture. Because the type
of aggregates in all the mixtures did not vary, the density
of the low-calcium fly ash-based geo-polymer concrete
varied only marginally between 2330 to 2430 kg/m3.

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V. R ATE ANALYSIS Higher concentration (in terms of molar) of sodium
hydroxide solution results in higher compressive strength
A. Cement Concrete (Grade M20)
of fly-ash based geo-polymer concrete and higher the
Quantity Amount ratio of sodium silicate-to-sodium hydroxide ratio by
Particulars Rate mass, higher is the compressive strength of fly ash based
(in Kg) (Rs.)
geo-polymer concrete, as the curing temperature in the
Cement 400 5.2 2080 range of 30C to 90C increases, the compressive
Fine strength of fly ash-based geo polymer concrete also
640 1000 420 increases, longer curing time, in the range of 4 to 96
Aggregate
hours (4 days), produces higher compressive strength of
Coarse fly ash-based geo-polymer concrete.
1280 1200 1008
Aggregate With the main objective of finding the effect of varied
Super concentrations of alkaline solutions on the strength
0.0044 75000 330 characteristics of the concrete, the test conducted, yielded
plasticizer
certain important findings from the material collected
Total 3838 from local vendors.
Note: All the rates are as per the standard rates in the In the process of conducting the test fly ash were
prevalent Indian market during the year 2012. procured from two different vendors which also led
to contrasting variation in the results. Thus,
B. Geo-polymer Concrete (Grade M20) highlighting the importance of choice of fly ash.
Quantity Amount Selection and grading of fine aggregate also played
Particulars Rate a major role. For a ratio of 0.67 (10mm: 20mm)
(in Kg) (Rs.)
Fine compressive strength of 26.67 N/mm2, and for the
640 1000 420 same molarity with a ratio of 0.42 comparatively
Aggregate
very low compressive strength was measured,
Coarse highlighting how important it is to select a proper
1280 1200 1008
Aggregate ratio for grading.
Super A general increase in the compressive strength with
0.0044 75 330 increase in the molarity was seen.
plasticizer
Importance of curing temperature also was clearly
NaOH 19.77 40 791 seen in the tests conducted. For test conducted at
25C, strength obtained was 0.872 N/mm2, while,
Na2SiO3 49.4 25 1235 on the contrary, for 80C it was 30.95 N/mm2.
Another important observation was that curing
Fly Ash 500 3.3 1650 under normal sunlight yielded strength of 16
N/mm2. This test was done in the month of
February 2012 in Sardar Vallabhbhai National
Total 5434
Institute of Technology, Surat(Gujarat) in India,
Note: All the rates are as per the standard rates in the where the ambient temperature was around 25 0C,
prevalent Indian market during the year 2012. hence, similar test when conducted in hotter months
can yield still better results. Thus, making insitu use
VI. D ISCUSSION of fly ash concrete a future possibility.
The main objective of this study was to find the effect Curing when done by wrapping with plastic bag
of varied concentrations of alkaline solutions on the gave better compressive strength as it preserves the
strength characteristics of the concrete. We expect that moisture.
the combined use of KOH and NaOH would help in In the rate analysis carried, it came out clearly with
achieving a more rigid structure and hence improve the the available resources fly ash based concrete is
strength characteristics. expensive than cement concrete and hence not
Based on the general finding, the following economical. However in the broader picture
conclusions were drawn: considering carbon credit, waste disposal and
limited availability of non-renewable resources,
geo-polymer concrete is sure to play major role in
construction industry.

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